mix 


UNIVERSITY  OF  ILLINOIS 


May  29 


.192.  A. 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

Harry—. Erana  i 3 _ _ ^JCataon 

entitled The use  _o f_  Sulphur  M on o_  Chi  or  i de  as _a_  Car  rier 

in  the  Production  of  Acid  Chlorides 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 

Bachelor  of  Science  in  Chemistry 
College  of  Liberal  Arts  and  Science 


DEGREE  OF 


500172 


. 


TABLE  Off  CONTENTS 

Pages 

Acknowledgment 

Preface---- 

Bibliography  and  Theoretical  Considerations  1-3 

Experimental  work • — 4-15 

Acetyl  Chloride 

Experiment  I 4 -5 

Experiment  II — 5-6 

Experiment  III — - — — 6-7 

Experiment  IV  — — ~ 7-8 

Experiment  VI 8-9 

Experiment  VII  - — — — - 9 

Experiment  VIII — -- — 9-1$) 

Experiment  IX  — -- 10  - 11 

Conclusion  — — ■ — -- — 12 

Benzoyl  Chloride 

Experiment  XI — — 13 

Experiment  XII 13 

Experiment  XIII  — - — — — v 13  - 14 

Conclusion  — 15 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/useofsulphurmonoOOwats 


PRRPACR 


The  work  was  undertaken  at  the  suggestion 
of  Professor  Adams  in  order  to  investigate  the 
practical  poss iblilities  of  the  method.  Some 
of  the  work  was  done  on  the  problem  at  Washing- 
ton, D.C.,  under  the  direction  of  Professor  Adams. 
The  investigations  were  carried  out  under  varing 
conditions;  the  practicability  of  the  process 
being  the  keynote  of  ail  the  work  done.  The  two 
acid  chlorides  which  were  investigated  were  acetyl 
chloride  and  benzoyl  chloride. 


BIBLIOGRAPHY  AND  THEORETICAL  COBSLDLiRATIQNS. 

A brief  account  is  given  in  Bulletin  de  la  Societe 
Chemque  188V,  Series  A,  page  145  of  the  interaction  between 
SC14  and  CHgCOgH  by  V.  Auger.  The  method  followed  being: 

A flask  in  which  one  mole  of  S^Clr,  and  two  moles  of  CHgOOgH 
was  cooled  with  ice  and  salt  ( tamp  era  tu  res  not  given). 

Chlorine  was  passed  into  the  mixture  until  no  more  chlorine 
was  absorbed,  when  the  flask  was  allowed  to  warm  up  to  room 
temperature.  The  free  sulfur  compounds  were  removed  by  shaking 
with  mercury  or  copper  powder.  The  mixture  was  then  distilled 
until  a boiling  point  of  60°  was  reached. 

The  yield  given  was  500  grams  of  acetyl  chloride  from 
600  grams  of  acid.  No  mention  is  made  of  S0gClP  in  the 
product. 

SCl^  is  only  stable  at  -19°  and  at  higher  temperatures 
an  equilibrium  exists  SC14  ; SCI#  -h  C1P. 

It  was  thought  that  at  10°  to  0°  the  reaction  would 
probably  progress  smoothly  without  too  high  a formation  of 
of  the  chlor  compounds  of  the  methyl  group.  The  reactions 
considered  were  the  reaction  of  SCl/u  present  in  small  amounts 
at  0°  to  10°  bringing  about  the  reaction 

2CH„C0oH  4-  SCI  — 2CH  C0C1+S0  + 2HC1 
O d 4b  O d 

The  additional  possiblility  of  the  reaction 

gCH  CO  H+SC1  4- Cl  2CH3C0C1  ^S02+2HC1  was 

2 2 2 2 


considered. 


, 


I 


. 


-a- 

Many  patents  have  been  taken  out  for  the  production  of 
(GHgGOjgO  from  CH^COQITa  and  S^Cl^  Cl^.  See  Chemical  Society 
Transactions  1909,  p.  1235;  1913  p.  1361-  Die  Berichte  1884 
p.  1286,  also  Thorpes  Dictionary  of  Applied  Chemistry:  Acetic 
Anhydride,  pages  27  -30,  Vol.  I,  1921  Edition. 

The  interaction  of  SO  Cl  -f  CK  GO  Ja  for  production  of 

d*  d O dt 

CHgCOgUa  is  quite  well  known.  A working  application  being 
given  in  German  Patent  ss6,  218,  1907. 

The  reaction  being  carried  out  at  20°  and  is  as  given 
2CH  COONa  -h  SO 0C10  — 2CH  C0C1 -f- 2EaCl  S0o  . In  the  presence 
of  an  excess  of  CEgCOglla  acetic  anhydride  is  formed. 

CHgCQQl'Ts  -t  CEgCOCl  (GHgCOjg-t-  EaCl 

In  all  trie  reactions  employed  for  the  production  of  acetic 
anhydride  using  either  the  S^Clg  or  the  oxychlor  compounds 
GH^GOGl  is  an  intermediate  compound. 

Reasoning  from  analogy  if  CH„GQ  H were  used  it  should 

d)  dj 

yield  a high  yield  of  CEgCOCl  and  a very  little  Acetic 
ari&ydride.  This  reasoning  proved  correct  as  is  shown  in  the 
experimental  work. 

The  production  of  benzyoyl  chloride  by  the  use  of  SgClg 
and  Clg  was  investigated  as  a similar  case.  The  low  rate  of 
activity  found  in  the  chlorination  was  probably  due  to  too 
107/  temperature,  the  gum  like  substance  v/as  a sulfur  organic 
compound  such  as  are  discussed  in  Journal  of  the  Chemical 
Society  1913,  page  1861.  The  type  of  compound  which  is  unstable 


, 


t 


-3- 


is  (0511500)22  . As  mentioned  in  the  Experimental  notes  this 
gum  like  substance  was  always  formed  and  disappeared  on 
standing . 


EXPERIMENTAL  v/ORK 


Experiment  I. 

A round  bottom  one  liter  flask  fitted  with  a three- hole 
rubber  stopper  v/as  used.  A glass  tube  conducted  the  chlorine 
into  the  mixture,  the  other  tube  was  provided  for  the  escape 
of  HG1;  a thermometer  was  placed  in  the  third  hole. 

Rive  moles  of  glacial  acetic  acid,  three  fourths  mole  of 
sulfur  monochloride  were  used.  Chlorine  v/as  conducted  into 
the  mixture  at  10°  for  eighteen  hours,  over  a six  day  period; 
considerable  excess  chlorine  was  used.  It  v/as  noticed  that 
the  red  color  of  the  SClg  v/as  discharged  upon  the  solution 
standing  and  reappeared  upon  leading  chlorine  into  the  mixture 
again.  At  the  end  of  the  chlorination  the  mixture  v/as  of  a 
light  yellow  color. 

The  fractions  (not  weighed)  were: 


1 st 

40  - 59° 

2nd 

60  - 120 

3rd 

120  - 140 

4 th 

140  - 155' 

S Cl  was  found  in  fraction  two  and  three.  The  method 
2 2 

used  being  pouring  a few  drops  of  the  liquid  in  ice  water 
in  which  case  free  sulphur  floats  as  a film.  In  later 
experiments  the  darkening  of  a bright  copper  wire  v/hen  dipped 
in  the  liquid  was  the  test  generally  used.  An  accident  rendered 
auantative  results  worthless. 


■ 


, 


. 


-5— 


The  boiling  points  of  the  possible  compounds  are: 


Monochloracetyl  chloride 

50.9° 

ilonochloractic  acid 

106° 

Dichloracetic  acid 

135-137° 

Trichloracetic  acid 

195° 

Dichloracetylehloride 

107  - 108 

Acetic  anhydride 

137.9° 

Sulphurmonochloride 

138° 

Sulphur  cLi  chloride 

59° 

Sulphurylchloride 

69.2° 

Experiment  II 

The  light  was  screened  from  the  chlorination  flash  in 
this  experiment  in  order  to  ascertain  if  light  was  the  catalyst 
which  caused  the  d6colori2ation  of  the  mixture  on  standing. 

The  mixture  used  was  3 l/E  moles  of  GKgCOgHand  l/£  mole 
of  S^Clo,  the  temperature  8°  - 10°.  Chlorine  was  passed  into 
the  mixture  for  16  hours  over  an  interval  of  four  days.  The 
decolorization  (due  to  SCI  ) was  not  prevented  by  excluding 
the  light  • 

The  mixture  was  fractionated  in  a two  bulb  column. 

The  fractions  were: 

1 st  fraction  40  - 60°  195  grams 

2 nd  ’ ' 60  - 119°  46  grams 

i » 


Tar-like  residue 


50 


. 


. * 


-6- 


The  first  cut  on  the  basis  CHgCOCl  theoretical  yield, 
showed  a yield  of  125  fo;  the  SGgCi^  found  in  the  distillate  e 
explained  the  overrun. 

The  presence  of  SOpClg  shown  by  pouring  the  mixture  in 

H2°: 

SO^Clg  2HgO  H2£04  HC1 

The  HrjSC^was  proven  by  BaCl^. 

Exp  er iment  III. 

The  possiblility  of  an  interaction  between  SOgClg,  SGlg 
end  CH^COgH  was  studied.  The  hypothetical  equation  is 

2 GHgCO^H  d-  S0^G1^4-  SClg  V 2 CHgCQCl-*-  2S0g-*-2HCl 

Three  and  one  half  moles  of  GHaGO-,H  and  one  half  mole 

5 2 

of  SgClg  were  cooled  to  zero  and  saturated  with  Gig,  one  mole 
of  SOgClg  was  then  added  and  the  temperature  allowed  to  rise 
to  room  temperature.  After  standing  for  thirty  hours  it  was 
again  distilled.  The  following  cuts  were  made: 


Eirst  fraction 

40  - 55° 

106 

Second  ' 1 

55  - 75° 

109 

Third  1 ' 

75  - 118° 

55 

fourth  1 ' 

118  - 188° 

55 

Residue 


68 


■ 


* 


' 


-7- 

A large  portion  of  cuts  one  and  two  proved  to  be  SO^Cl^. 
Gonolusi on:  Under  the  conditions  of  the  experiment  the 

interaction  between  S^Clg  ^E^CO^E  °ceured  to 

only  a slight  extent. 

Experiment  IV 

This  experiment  was  made  to  determine  the  quality  of  the 

product  formed  when  a large  amount  of  SOI4  was  present. 

Three  and  one  half  moles  of  CH„C0oH  and  one  half  mole  of 

3 c 

SgClg  were  cooled  as  rapidly  as  possible  without  freezing  out 
too  much  acetic  acid  down  -19°.  It  was  possible  to  cool  down 
without  entire  solidification  as  the  eutectic  point  was 
lowered  by  the  formation  of  the  chlorcompounds  as  chlorine  was 
led  into  the  mixture.  The  final  cooling  was  done  with  CaClr 

Cj 

and  ice.  The  mixture  was  saturated  with  Cl  at  -19°  and  left 
well  packed  in  salt  and  ice  over  night  to  permit  the  completion 
of  the  reaction. 

SCI4  -f-  2 CE3CO2H  — 2 CH3CO01  2EC1 -+-S02 

The  next  day  the  mixture  was  again  cooled  to  -17°  and 
saturated  with  Cl  . The  mixture  stood  for  24  hours  and  was 

Cj 

distilled. 

Eirst  Gut  45°  - 80°  133  grams 

35,1  of  the  material  boiled  between  45  - 60°.  No  SgClo  was 

found  in  the  distillate.  Large  amounts  of  SO^Cl^  were  given 
off  in  distillation. 


1 


-8- 

Second  Gut  80  - 123°  42  grams 

Ilinely  per  cent  boiled  between  118°  - 120°. 

Weight  of  escaping  gas  and  loss  50  grams 

Weight  of  fractions  dnd  residues  recovered  290  grams. 

A test  was  made  on  the  third  fraction  by  oxidizing  with  KNOg 
under  a reflux,  and  HgSO^  was  formed  proving  the  presence  of  or- 
ganic sulfur  in  this  fraction* 

Experiment  VI 

This  experiment  was  made  to  obtain  additional  data 
regarding  the  possible  reaction: 

2CH5G02H  f SO 2C1  £+SCl4  — h 2CiigC0Ql  f 2S0g  4-  2HC1 
One  fourth  mole  of  S^Clg  and  one  half  mole  of  SOgClg 
were  saturated  with  Gig  at  0°  to  -6°  in  order  to  change  SgClg 
to  SClg. 

Three  moles  of  CH^CQ^H  was  then  added,  the  mixture  was 

o 2 

allowed  to  warm  up  in  an  ice  salt  bath  to  room  temperature  in 
twenty- four  hours.  It  was  again  saturated  with  Gig  at  Oo-  6° 
and  left  for  twenty  hours  as  before. 

SgGjlg  and  SClg  were  absent  in  the  mixture  as  shown  by  test. 
The  mixture  weighed  235  grams. 

Weight  of  Distillate  40°  - 80°  100  grams. 

11  11  residue  125  1 ' 

SOgClg  in  distillate  59.27  ’ 1 

This  shows  40.7$  CH^GOCl  formed  in  the  first  cut. 

Conclusion  : The  reaction  of  SOgClg  and  SgC^with  CHgCOgH  is 


^illl 

, 


-9- 


not  a practical  one,  altho  an  interesting  possibility. 


Experiment  VII 


This  experiment  was  made  to  check  data  at  0°  - 15G^ . 
The  mixture  used  was  3 1/2  moles  of  CH^CO^H 


? i 


i i 


ID  3 1 


l/2  mole  of  SgClg 
The  chlorination  was  carried  on  in  diffused  light.  A 
very  slow  stream  of  chlorine  was  led  into  the  mixture.  Six 
hours  of  chlorination  used  up  the  S^Glg* 

The  weight  of  the  mixture  was  305  grams 
The  weight  of  the  first  fraction  40°  - 75°  was  SO  grams 

75  - 118°  "33  " 


1 1 


1 1 


1 1 1 1 


1 1 


1 1 


Two  thirds  of  the  33  grams  came  over  between  106°  - 112° 
showing  the  presence  of  chloracetylchlorides. 

Third  fraction  116°  - 123°  Acetic  acid  68  grams 


Fourth  .Fraction  123°  - 150°  53  ' ' 

The  loss  due  gas  and  volatility  was  69  grams  (305  - 236) 
Conclusion:  Under  the  conditions  best  suited  to  a commercial 

production  the  experiment  shows  a poor  yield  of  CH^CQCl  and 
a high  formation  of  undesired  higher  chlor  bodies. 

Experiment  VIII 

Experiment  made  to  determine  the  results  to  be  expected 
at  room  temperature  chlorination. 

The  proportions  were  the  same  as  in  the  former  experiments, 
viz:  3 l/2  moles  of  Ch^GOgH  and  l/2  mole  of 


■ 


' 


' 


-10- 

Chlorine  was  passed  into  the  mixture  slowly,  the  chlorination 
took  ten  hours,  and  occupied  three  days.  The  finished  chlorin- 
ated mixture  was  allowed  to  stand  at  room  temperature  connected 
to  a water  cooled  reflux  condenser  for  twenty  four  hours  to  allow 
the  escape  of  the  gasses. 


It  was  fractionate: 


first  Cut 

0 

o 

1 

CD 

o 

o 

63 

grams 

Second  ' 1 

1 

o 

o 

CO 

125° 

27 

» 1 

Third  ' ' 

125°  - 

140° 

76 

i i 

Residue  estimated 

50 

SO^Cl^  found  in  first  cut  42.1$ 

Conclusi on:  The  fractions  obtained  do  not  show  any  very  high 

increase  in  chloraeetic  or  chloracetyl  chloride  at  a higher 
temperature,  but  the  yield  of  acetyl  chloride  is  very  low  and 
tar  residue  high. 

Experiment  IX 

This  experiment  was  made  to  determine  the  effect  of  a 

higher  concentration  of  S Cl  over  the  acetic  present  in  the 

2 2 

mixture. 

One  half  mole  of  SoClg  was  used  and  one  mole  of  glacifl.1 
acetic;  the  mixture  was  cooled  to  -5°  to  -12°  while  chlorine 
was  passed  into  the  mixture,  until  the  evolution  of  HC1  slowed 
down.  Then  l/2  moles  of  additional  CH^CO^H  was  added  and  Cl 


. 


-11- 

pass  e&  in  until  the  HG1  given  off  became  noticeably  less,  when 

another  l/2  mole  of  Cl  CO  H was  added.  Unpon  standing  over 

3 2 

night  the  SClg  color  was  completey  discharged. 

The  mixture  was  fractionate: 


First  Fraction 

30°  - 75° 

186  grams 

Second  1 ' 

75°  - 118° 

8 ' ’ 

Third  Fraction 

118°  - 125° 

11 

Fourth  ' ' 

125°  - 140° 

not  weighed 

Fifth  ' 1 

140°  - 175° 

22  grams 

Residue  tar 

The  fifth  fraction  gave  a yield  of  10  grams  of  monochlor  acetic 
acid. 

The  first  fraction  was  again  fractionated  in  a column, 

177^  grams  being  taken. 

First  Gut  35  - 55°  126  grams 

Residue  in  distilling  flask  28  grams 

154  1 * 

Loss  due  to  gas  given  off  and  volatility  loss  from  the 
receiver  23  grams. 

The  fa  SQgGlg  in  the  126  grams  cut  was  37.2  >0 — 36.9 % 

This  shows  an  indicated  yield  of  53.6 fo  CEgCOCi  on  theory 
of  CH^COgH. 

Gonclusi on:  This  experiment  shows  the  most  interesting 

possiblili ties  for  the  production  of  CH^COCl  from 
But  the  high  'fo  of  SO^Cl^  makes  the  product  obtained  valueless. 


I 


-12- 

C on  elusion 

In  as  much  as  the  problem  was  one  in  which  the  interest 

was  largely  in  the  practical  possibilities  of  using  S^Gl^ 

rather  than  PQl^  as  a chlorine  carrier  to  produce  acetyl 

chloride,  it  was  proven  impractical. 

The  yield  of  acetyl  chloride  in  Experiments  IV  and  IK 

are  such  as  to  male  it  profitable  to  produce  acetyl  chloride 

in  this  manner,  provided  a method  may  be  devised  to  easily 

and  cheaply  remove  the  SO  Cl  from  the  product.  Experiment 

2 £ 

IV  is  of  much  less  value  as  a practical  method,  owing  to  the 
low  temperature  at  which  the  reaction  was  carried  on;  this 
objection  does  not  hold  for  Experiment  IK. 


. 


-13- 


Exp  eriment  XI 


The  chlorination  of  Benzoic  Acid  to  Benzoyl  Chloride, 
The  chlorination  was  done  at  room  temperature.  Three 
hundred  and  fifty  c.c.  of  CC1  was  used  as  a solvent,  or 
dilutent  into  which  was  charged  1££  grams  of  benzoic  acid 
(one  mole)  and  i/3  mole  of  S^Cl^*  The  equation  of  the 
desired  reaction  being: 


co2e 


V 


-CQCl 


+ S£C1£  ^3D1£ 


-+  4HC1 


2S0, 


The  rate  of  chlorination  was  very  slow;  many  troublesome 
stoppages  of  the  chlorination  tube  was  caused  by  a gum-like 
deposit  which  formed  in  and  about  the  inlet  tube.  After 
several  at  tents  the  experiment  was  discontinued. 

Experiment  XII 

This  experiment  was  also  made  using  CC14  as  a dilutent 
sovent,  350  c.c.  being  used.  The  benzoic  acid  was  added  in 
small  portions  in  order  to  prevent  the  fomation  of  the  gum- 
like material.  After  17  grams  had  been  added  the  gum- like 
substance  prevented  further  admission  of  Cl  . Very  little 
HC1  was  given  off  at  the  time  and  evidence  showed  very  little 
chlorinati on. 


Experiment  XIII 


The  solvent  dilutent  chsen  in  this  experiment  was  benzc^l 


-14- 


chloride,  as  it  was  thought  that  the  presence  of  the  benzoyl 
chloride  might  act  as  a catalyst.  One  hundred  and  thirty- 
seven  grains  of  benzoyl  chloride  and  l/8  mole  (17  grams)  of 
SgClg  were  placed  in  the  flask;  the  benzoic  acid  was  added  in 
ten-gram  portions  during  an  interval  of  eight  days#  The  ab- 
sorption of  chlorine  was  veiy  slow.  Tho  time  during  which 
chlorination  was  extended  was  thirty- four  hours,  chlorine 
being  conducted  into  the  solution  for  this  time. 

The  disappearace  of  the  benzoic  acid  from  the  mixture 
was  taken  as  an  indication  of  its  chlorination.  Sixty  grams 
of  benzoic  acid  were  used. 

The  mixture  was  distilled,  a large  amount  of  HG1  being 
given  off,  up  to  150°. 

ITirst  fraction  190°- 195°  weighed  109  grams 

Second  1 1 195°- 205°  1 1 56  grams 

Tar- like  residue  53  11 

Deducting  the  original  amount  of  benzoyl  chloride  added 
the  yield  was  28  grams  or  43.4$  of  the  crude  material. 

Boiling  point  Benzoyl  chloride  199° 

Boiling  point  Benzoic  anhydride  360° 


, 


-15- 


Conclusi on 

The  chlorination  of  benzoic  acid  at  room  temperatures 
using  SgClg  as  a carrier  is  not  a practical  tiling.  The 
Experiment  XIII  showed  the  yield  and  the  very  slow  rate  of 
chlorination  to  make  it  an  unprofitable  thing  under  the 
conditions  of  the  experiment.  Other  lines  of  research  were 
taken  up  and  the  possible  chlorination  of  benzoid  acid  using 
SgClg  as  a carrier  at  higher  temperatures  was  not  tried. 


